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Патент USA US2405996

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Patented Aug. 20, 1946
2,405,996
UNi'i‘ED STATES PATENT OFFICE
2,405,996
PROCESS OF AVERAGING HYDROCARBON S
Robert E. Burk, Cleveland Heights, Ohio, assign
or to The Standard Oil Company, Cleveland,
Ohio, a corporation of Ohio
No Drawing. Application April 5, 1944,
Serial No. 529,681 ,
20 Claims.
(Cl. 196—--9)
1
2
This invention relates to the treatment of light
and heavier molecular weight hydrocarbons with
a catalyst comprising primarily hydrogen ?uoride
promoted by a minor proportion of boron tri?uo
ride to produce hydrocarbons of intermediate U!
carbon, such as n-butane or n-pentane in excess
of that entering into the reaction, fractionating
the excess to remove all or a portion of the iso
mer which is formed during the averaging re
molecular Weight, a process herein termed “aver
action, and recycling the unisomerized normal
hydrocarbon together with any portion of the iso
aging.”
mer not fractionated.
.
A preferred and important embodiment of the
An additional object of the invention is to carry
invention comprises the use of n-butane as the
out the averaging process under conditions of
light hydrocarbon, and a liquid hydrocarbon boil 30 temperature and pres-sure not lower nor higher
ing above the gasoline range as the heavier hy
than can be obtained conveniently in ordinary
drocarbon, to produce gasoline of desirable prop
plant operations,
erties.
.
The invention has as a. further object the pro
It is one of the objects of the invention to
vision of a process of the character described in
utilize the relatively unreactive normal hydro
15 which the activity of the catalyst, in addition to
carbons, such as n-butane, as one of the raw ma
being controlled by variations in temperature,
pressure and other factors‘ ordinarily employed
in catalytic operations, also can be controlled
terials in making more valuable hydrocarbon
products.
A further object of the invention is to utilize
readily by means of the partial pressure and
heavier hydrocarbon fractions, such as kerosene 20 boron trifluoride constituent of the catalyst.
or naphthas, in the formation of hydro-carbons
Still a further object is the provision of a proc
of lower molecular weight, such as gasoline, with
ess of averaging as described in which the cata
out the production of large amounts of unsatu
lyst can be readily recovered and reused.
rates or ?xed gases, and also without the de
Other objects of the invention will appear from
the following description.
structive in?uences and losses incident to con
ventional methods of cracking.
In carrying out the process of the invention a
It is also an object of the invention to provide
light hydrocarbon, such as butane, is mixed with
a process in which a Wide variety of light and
the heavier boiling fraction, such as a normally
heavier stocks of diverse nature may be used as
liquid'hydrocarbon. These are caused to react
the raw materials.
preferably in a liquid state, in the presence of a
:An additional object of the invention is to uti
liquid catalyst and under conditions of tempera
lize both a light hydrocarbon and a heavier hy
ture and pressure as will be pointed out more
drocarbon simultaneously in a single reaction to
particularly hereinafter, to produce products
produce valuable products resulting from a net
heavier than the light hydrocarbon and lighter
consumption of both of them at the same time.
than the heavier hydrocarbon starting materials.
Still a further object of the invention is to
At the conclusion of the treatment the hydrocar
carry out the above reactions in the liquid phase
bons are separated as one phase and may be frac
in the presence of a liquid catalyst comprising
tionated, and the catalyst is separated as another
primarily hydrogen ?uoride and promoted by a
phase. The catalyst phase may be reused as such
minor proportion of boron trifluoride, and if de J. (l or may be regenerated and reused.
sired, also promoted by the presence of an un
The light hydrocarbon may be methane
saturate.
through hexanes, preferably propane through
Another object is the provision of a process in
hexane. Methane and ethane are more di?icult
which fluorides containing the impurities present
to react. If the operation is to be in the liquid
in commercial grades may be used.
1 phase the difficulty in liquefying ethane and
Still another object of the invention is to carry
methane also suggests that they would be less
out the averaging reaction in the presence of an
desirable for practicing the invention on a com
amount of the light hydrocarbon in excess of that
mercial scale. Pentanes and butanes are pre
entering into the reaction so as to form products
ferred, especially the latter. Mixed propane and
of enhanced value, and in which the excess of the 50 butanes and mixed butanes and pentanes may
lower molecular weight hydrocarbon may be re
be used, or all three in admixture. Pentanes and
cycled to the averaging reaction in a continuous
hexanes are reasonably valuable as such, or can
or semi-continuous process.
A further object of the invention is to carry
out the above process, utilizing a normal hydro
be
used
advantageously in ‘ other
processes.
Butane is readily reacted in accordance With‘the
55 invention and since it is not suitable in itself as
2,405,996
3
4
.
a motor fuel and there is an ample amount, the
invention assumes particular importance with
reference to its use as the lower molecular weight
tion boiling over a broader range. The stock to
be operated on in a commercial embodiment will
raw material. For this reason the invention will
be described employing butane as an illustrative
pend largely on the economics involved. For ex
example.
,_
‘
depend upon a number of factors and may de
ample, if a plant is equipped to practice iso
merization, that process may be practiced on
certain light fractions and the heavier stocks
may be averaged. Other stocks may be pre
The light hydrocarbon may be obtained from
natural gas or from any re?nery operation; it
ferred for operating existing catalytic cracking
is immaterial if it contains small amounts of
other constituents, and for this reason it need 10 units and the remainder may be used in aver
aging. The versatility of the process with ref
not be highly puri?ed. It is also immaterial, and
erence to the stocks that may be employed is an
in fact it is an advantage as .pointed out later,
important advantage of the process of the in
if it contains a small amount, of unsaturates.
For this reason it is not necessary to fractionate
~ vention.
The ratio of the light to the heavier fraction
the unsaturates and other ingredients from the
may vary over a relatively wide range. In the
light fraction. When a butane fraction is used,
case‘ of averaging with butane, it is more di?icult
it may comprise normal butane, but no harm is
to obtain a net consumption of the light fraction,
done if isobutane is present. Under some condi
when less than 1 mol of the light fraction per
tions the reaction is facilitated by the presence
of isobutane. However, since isobutane is useful 20 mol of the heavier fraction is used as raw mate
rials, except when other variables are very closely
in other reactions, such as alkylation, the ability
controlled. Contrary to what might be expected,
to use normal butane as the starting material in
a corresponding increase in yield is not obtained
the averaging process is of great importance.’ If
with a, pronounced increase in the light fraction.
the process is practiced with pentanes or hexanes
It has been found that with 2 to 6 mols of the
as the light hydrocarbon, the ‘ability to use the
light fraction per mol of the heavier fraction the
normal hydrocarbon similarly is an important
reaction gives maximum yield and maximum con
sumption of the light fraction. Less than 3 mols
,In a continuous operation in whichjan excess
gives somewhat lower yields, but this disadvan
of butane is used, a part of the excess may be
isomerized to isobutane. When the excess butane 30 tage may be offset by the advantage incident to
lower amounts of the excess that need be recycled.
is recycled the amount of isobutane in the re
Since the yields do not improve markedly when
cycled fraction may be varied and this becomes
more than 8 mols of the light fraction is used,
a ‘controllable variable. Larger amounts of iso
there is no object in having'present more of this
butane are helpful, under some conditions, in
advantage.
.
producing higher yields. _
_
.
z
"
-'
_
The heavier fraction should be selected with
reference to the light hydrocarbons. . In .general
the heavier fraction should have at least vtwo
fraction than will re?ect an improvement, since
there is no point in recycling a large excess which
does not accomplish a corresponding improve
ment in the reaction.
more carbon atoms than the light hydrocarbons.
For example, propane may be averaged with
pentane or any heavier hydrocarbon‘; Butane
The catalyst used in the process comprises hy
drogen ?uoride promoted with a minor proportion
of boron trifluoride therein,and in some instances
may be averaged with hexane or any heavier hy
with an ole?n.
drocarbon.
phase.
Generally the heavier fraction will
have a molecular weight higher than hexane.
It is used preferably in the liquid
7
-
' Hydrogen ?uoride boils at about 67° F. and is
therefore a liquid at temperatures just under
room temperature and may be kept liquid at
higher temperatures by moderate pressures. The
natural gasoline, light naphtha (‘YO-300° F),
temperatures and pressures used in the process of
heavier naphthas (250—400° F.), kerosenes (350
the invention are conveniently those that main‘
550° F.), light gas oils MOO-625°), heavy gas
oils (500-710" F.), mixtures of light and heavy 50 tain the hydrogen ?uoride liquid. Boron tri
?uoride boils at —l50° F. and is a gas at the tem
gas oils (400-710" F), deasphaltized'and dearo
peratures and pressures conveniently employed in
matized residues (above 700° F.) , the portion of
hydrocarbon treating processes. However, boron
crude boiling to 550° F., the portion of crude boil
trifluoride dissolves in liquid hydrogen ?uoride
ing to 700° F., the portion of crude oil boiling
between 250-"110n F., mixtures of natural .gaso- ; to a given extent and the amount which dissolves
at any given temperature depends on the partial
line, or naphthas with kerosenes and fractions
pressure of boron tri?uoride. At higher partial
boiling higher than 825° F. ‘ Other stocks that
pressures, a larger amount of boron trifluorid‘eis
may be used are Fischer-Tropsch (Hz-l-CO)
dissolved.
stock, Houdry cycle stock and thermal cycle stock.
The boron trifluoride in the hydrogen ?uoride
Some of the above fractions may require, aro 60
in the liquid phase possibly may react at least
matic extraction because the stock should be rela
to some extent, but an understanding of the
tively low in aromatics as explained hereinafter.
chemistry involved is not necessary to practice
The heavier fractions described may contain nor
my invention, and I do not intend to be bound by
mal hydrocarbons, isomers, naphthenes or small
any theory. At any eventv the amount of the
amounts of other hydrocarbons otherthan nor
boron tri?uoride in the hydrogen fluoride, which
mal or unsaturates. The ‘latter may be bene
controls the activity of the catalyst, is a function
?cial as mentioned heretofore.
I. Q
of the partial pressure of the boron tri?uoride.
In some instances both the light and. the heav
The amount of boron trifluoride dissolved in
ier fractions to be reacted in the averaging proc
the hydrogen ?uoride, at any given temperature,
ess may be in the form of a single fraction. vFor
may be expressed conveniently in terms. of the
example, a stock boiling from .70‘? to above 350°
partial
pressure of boron tri?uoride. This may
F., or crude oil or reduced crudeL as, such, may be
vary, in accordance with the invention, from 5 to
averaged. Since the averaging oi‘heavie'r hydro
While the heavier fraction may be a pure hydro- . ;
carbon, generally it will be a mixture, such as
carbons tends to promotethe averaging‘of lighter
hydrocarbons, it may be desirable to use a frac
1000 pounds per square inch; generally ,about50
to 300 pounds per square inch will be used. How
2,405,998
5
ever, the partial pressure should under no cir
cumstances be such that the amount of boron
tri?uoride exceeds 50 mol per cent of the ?uorides.
With the partial pressures usually used the
.
6
may also have a bene?cial effect in causing some
of the hydrocarbons to shift from the catalyst
phase of the reaction to the hydrocarbon phase.
The amount of the catalyst employed must be
amount does not exceed 25 mol per cent. The 5 considered with reference to both of the fluoride
words “dissolved” and “solution” are used as
ingredients comprising it. The amount of the
generic to both a physical admixture and a reac
hydrogen ?uoride may be 5 to 300 volume per
tion product.
cent based on the hydrocarbons to be treated
One of the advantages of the process of the in
when in liquid form, preferably the amount
vention is the ability to control the reaction by
should be about 25 to 100 volume per cent.
adjusting :the activity of the catalyst through con
trol of its composition. This may be accom
plished by varying the partial pressure of the
Amounts as low as 1 volume per cent may be used
boron tri?uoride, because a change in this partial
amounts increases the rate of conversion and
in a multistage treatment in which the total
would be at least 5%. The use of larger
pressure results in a change in the amount of 15 the yield in a given time under conditions
boron tri?uoride dissolved. If the partial pres
otherwise the same. The yield drops somewhat
sure of the boron tri?uoride is increased, by ad
with a decrease in the amount of hydrogen fluo
mitting boron tri?uoride to the reaction zone from
ride. In view of this fact the amount used
a high pressure source of supply, the activity of
may depend to a large extent upon the eco
the catalyst is greater under conditions other 20 nomics involved and the maximum conversion
wise the same. If this partial pressure is de
desired per pass of the material. The total
creased, by bleeding boron tri?uoride, the activity
amount necessary may also be less if it is
of the catalyst is reduced.
supplied in increments during the reaction. If
If an ole?n is added, or is present in the reac~
desired the used catalyst may be removed before
tion zone in an amount less than that which acts 25 the next increment is supplied.
as a poison, the ole?n appears to act as a pro
The amount of the boron fluoride used, as ex
moter. The available evidence indicates that the
ole?n acts as a “hydrogen acceptor” and that the
hydrogen ?uoride-boron trifluoride solution or
the reaction product may form a new compound 30
pressed in terms of partial pressure, has been
indicated heretofore in describing the composi
tion of the catalyst.
When an ole?n is added separately as an in
or chemical complex with the ole?n. Since ole
gredient it may Vary from extremely small
?ns may be formed in the process, especially
amounts to 100 or more mol per cent based on
when heavier stocks are used, the addition of an
the amount of the boron tri?uoride dissolved in
ole?n as a separate added ingredient to the stocks
the hydrogen ?uoride. Expressed in practical
may not reflect a separate improvement.
35 terms, the amount of the ole?n may be 1/2 to 25%
The catalyst to be used in practicing the in
based on the hydrocarbons being treated.
vention, therefore, may be viewed as hydrogen
The total pressure should be su?icient to keep
?uoride promoted by a minor proportion of boron
the hydrogen ?uoride in the liquid phase, and
tri?uoride; or it may be viewed as hydrogen ?uo
preferably also to keep all the hydrocarbons in
ride promoted by both boron trifluoride and an 40 the liquid phase. It must, of course, exceed the
ole?n; or a combination of both ?uorides pro
partial pressure of the boron tri?uoride. The
moted by the ole?n. The presence of an ole?n
total pressure may vary up to 1000 pounds per
generally gives somewhat better results.
square inch, such as might be obtained by the
The hydrogen ?uoride and boron tri?uoride
presence of an inert gas, but generally no ad
may be the available commercial grades. It is 45 vantage is gained (unless hydrogen is used as
not necessary to have chemically pure ?uorides.
described later) by having a total pressure
The impurities in the commercial grades, in
greater than the sum of the partial pressure of
cluding water, which are generally present in an
the boron tri?uoride and the partial pressures
amount of about 1A; to 5 per cent, do not inter
of the hydrogen ?uoride and the hydrocarbons
fere materially withthe operation of the cata 50 at the temperature utilized.
lyst. In view of the economic advantage of
The time of contact between the hydrocarbon
using the commercial grade, it is preferred, and
and the catalyst may vary with the tempera
was used in the following examples. Reference
ture, thoroughness of contact or mixing between
to the ?uorides hereinafter is intended to in
the hydrocarbon and the catalyst, and other fac
clude such commercial grades and their normal 56 tors. Depending upon such other factors, the
impurities or their equivalent in composition.
time should be selected to give optimum yields.
The conditions under which the process is
This may be from 5 minutes to 3 hours, although
carried out are selected within convenient ranges
in the higher temperature ranges and with very
so as to produce maximum yields. In general
thorough mixing, as might be accomplished with
the temperature may vary from —30° to 400° F.,
preferably from about 20° to 212° F. Averaging 60 the best commercial mixing apparatus available,
the time might be reduced to the order of a min
with kerosene as the heavier stock shows that
ute. In a commercial operation, it is desirable,
the process can be carried out conveniently at a
of course, to keep the reaction time as short as
temperature within a range of about 20° to 150°
F. It is an advantage of the process that ex 65 possible since this decreases the size of the re
actor necessary to produce a given amount of
treme temperatures in either direction are not
necessary. A single temperature may be used
product. Observations indicate that the reac
throughout the reaction, or it may be varied dur
tion proceeds quite quickly, and readily reaches
ing the reaction. If the catalyst is reused a
a condition where more time does not materially
somewhat higher temperature may be desirable
alter the distribution of the products to such
than is the case when the catalyst is fresher. It
an extent that it is of economic advantage to
may be desirable, for this reason, to operate with
continue the reaction longer.
ascending temperatures in the direction of ?ow.
The agitation may be accomplished with any
This may enable a reduction in the amount of
type of a mechanical agitator or stirrer, or it
catalyst per unit of the product formed, and it 75 may be accomplished by induced ?ow such as by
2,405,996
the introduction of one of the ingredients from
an ori?ce under high pressure.
The temperature, composition of the catalyst,
time of contact, and other factors mentioned
8
In‘ either a batch or continuous process, the ?uo
rides may be introduced in increments at differ
ent intervals during the total reaction period.
alyst to obtain the identical result. For example,
When using a continuous mixer having a plu
rality of stages, the ?uorides may be introduced
at each stage. The operation may be counter
current or concurrent.
After the hydrocarbons and the catalyst have
been mixed under the selected conditions for the
time. Thus, for example, any temperature with~
separating operation is carried out under the
by adjusting‘the partial pressure of the boron
Certain hydrocarbons, notably unsaturates
and aromatics, tend to accumulate in the catalyst
heretofore are more or less interdependent. The
ranges described heretofore are not intended to
mean that any temperature'may be used with
any length of time or any composition of cat
desired time, the agitation will be discontinued
if a lower temperature is used, a somewhat larger
and the catalyst phase and the hydrocarbon
amount of catalyst may be present or a somewhat
phase, being mutually insoluble in each other, will
higher partial pressure of boron tri?uoride may
separate by gravity. If desired, forces greater
be used, or the treating time may be longer, or
than gravity, such as centrifuging, can be used
mixing better, or any or all of them, to obtain
about the same result that would be obtained 15 in effecting the separation. The lighter or upper
layer will contain the averaged hydrocarbons and
with a higher temperature‘ and with a lesser
the unreacted raw materials, and the lower layer
amount of catalyst, or a lower partial pressure
will comprise the catalyst phase. Preferably this
of boron tri?uoride, or with a shorter treating
in the range may be employed and the other 20 pressure used in effecting the reaction.
If ?uorides are separated from the hydrocar
variables may be adjusted within their ranges so
bons at such a temperature and pressure that the
as to obtain averaging.
catalyst remains as a distinct liquid phase, in
It is a particularly important part of the proc
accordance with the preferred embodiment, the
ass that in addition to varying the time of con
catalyst phase may be recycled and reused alone
tact, the amount of catalyst, and the tempera
for the treatment of a fresh supply of raw ma
ture, which are the variables with which the
terials or in admixture with a fresh supply of the
prior art has had to work, it is possible, in accord
catalyst, such as in a countercurrent system. The
ance with the process to vary the composition of
used catalyst may also be employed in other aver
the catalyst by varying the partial pressure of
aging operations which require a less active cat
the boron ?uoride. Thus, for any given temper
alyst. For example, the catalyst may be used
ature, time of contact, etc., at which it is desir
initially on a stock which is di?‘icult to react
able to operate because of plant equipment or
and after separation from said stock, it may be
economic reasons, the rate of. the reaction and
reused with stocks that are easier to react.
the activity for the catalyst can be varied simply
tri?uoride.
.
The process may also be carried out in the
presence‘of hydrogen, which may be introduced
into the reaction in an amount to provide a par
phase in the form of a complex during the av
eraging reaction. A small amount of a complex
with an unsaturate is thought to be helpful as
tial pressure of hydrogen of 100 to 1000 pounds per 40 a promoter, and for this reason the presence
of an ole?n has been indicated as desirable. But
square inch. This tends to minimize the amount
the accumulation of too much hydrocarbon in
of hydrocarbons entering the lower layer.
the catalyst phase exerts a poisoning effect.
The process is adapted either for batch opera
Therefore, if the amount of hydrocarbon in the
tion or for continuous operation. In either type
catalyst phase is kept at the optimum value, the
of operation the feed stocks may be dried, if
reaction will proceed more rapidly and less of
desired, by suitable driers. In a batch opera
the catalyst will be required. To overcome this
tion the hydrocarbons and the ?uorides are
poisoning effect, a part or all of the used or re
brought together in the desired amounts in a
used catalyst may be withdrawn at any stage of
closed container or autoclave where they are pref erably subjected to agitation and maintained un 50 the operation and subjected to a relatively high
temperature, for example, 250-600" F. This may
der the desired temperature and pressure for
be by way of a pot still, or by means of ?ashdis
the required length of time, In a continuous
tillation. Preferably a two-stage treatment is
process the ?uorides and the hydrocarbons to
employed, the ?rst stage using a ?ash distilla
be treated are fed into a continuous type mixer,
tion at a somewhat lower temperature, followed
for example, a three-stage mixer, and main
by distillation in a stripper at a higher tempera
tained at the desired temperature and under
ture. At this temperature substantially all of
the appropriate pressure. 'The ?ow through the
the ?uorides are liberated as gases, These can
mixer may be intermittent or continuous and
be collected and condensed and/or compressed
may be adjusted so that the hydrocarbons are
in contact with the catalyst for the desired length 60 and returned to the mixing zone or stored or
otherwise used.
of time.
Alternatively, instead of distilling the ?uorides,
In either the batch or continuous operation, if
the lower layer or catalyst phase may be treated
an ole?n is to be added as a promoter, this may
with a material which exerts a solvent action on
be containedv in either of the raw materials or
may be introduced separately or absorbed in the 65 the ?uorides and which is immiscible with the
hydrocarbons in the lower layer, or which forms
?uorides. If hydrogen is to be used, this may be
a chemical compound or complex with the ?u
introduced from a separate high pressure source
orides, and from which the ?uorides may be re
of the supply.
leased later, for example, by heating. It may also
The order of mixing the components is not
critical. The light and heavy hydrocarbons may 70 be possible to introduce this material into the
catalyst phase before separation, whereupon the
be fed separately or mixed and introduced into
hydrocarbons in the catalyst phase would be
the ?uorides or vice .versa. Alternatively the
shifted to the hydrocarbon phase.
light component may be mixed with the ?uorides
Another alternative is to distill off a part or
and this mixture fed gradually to the heavier
most of the ?uorides from the lower layer'at‘ a
hydrocarbons or vice versa in‘ one or more'stages.
2,405,996
10
relatively lower temperature and remove the
rest of the ?uorides by extraction with such a
material. Substantially all of the ?uorides can
be recovered by any of these processes and reused.
\
ferred to the lower layer and form a complex
with the catalyst and thus decrease its activity.
For this reason it is desirable that feed stock
should contain a minimum of aromatics. While
The hydrocarbons in the upper layer can be
it is not essential that the stock be, free from
treated with a material to extract ?uorides there
aromatics if other conditions are adjusted suit
from if this is desired, for example, an oxyfluo
ably, it will be generally preferable to reduce the
boric acid, such as H3BF202 or I-I4BF3O2.
aromatic content of the stock of a dearomatiza
The upper phase from the separation, compris
tion process. This may be done by any means
ing the hydrocarbons, may be sent to a primary 10 ‘conventional in the art, such as solvent extrac
fractionating column and the excess of butanes
tion, or the ?uorides may be used for dearomatiz
and any ?uorides dissolved in the upper phase
ing in accordance with the process described in
may be separated at the top of the column‘ and
my Patent No. 2,343,744, granted March 7, 1944.
recycled to the reaction zone. Since an excess of
In a multiple treatment process the ?rst treat
butanes in the reaction zone is preferable, a part
ment with the catalyst may be largely one of de
of the feed may comprise the recycled butanes
aromatizing and subsequent treatments may be
fraction and fresh feed. The amount of the
responsible for the major portion of the averag
fresh feed stock need be only equal to that which
ing reaction. Although the catalyst may be re
is consumed in the averaging reaction.
duced in activity during the averaging reaction
During the averaging process the normal 20 so as to render it ineffective for further averag
butane fed into the averaging reaction zone may
ing, it may still be used to dearomatize and the
become at least partially isomerized and the
dearomatization of the feed stock with the used
butanes that are taken from the top of the
catalyst from the averaging reaction is an im
primary fractionating column may be further
portant aspect of the invention. This could be
fractionated in a secondary fractionating column 25 accomplished, fOr example, in a two-stage coun
to separate a portion or all of the isobutane for
tercurrent treatment. The catalyst containing
use in other processes, such as alkylation, and
the aromatics may then be subjected to a re
the remainder of the excess of the butane frac
generating action in accordance with any of the
tion may be returned to the averaging zone. Thus
processes indicated heretofore, and the ?uorides
the invention contemplates the ability not only
returned to the averaging zone.
>
to utilize the normal butane and convert it into
For example, the lower layer from a ?rst stage
a higher molecular weight hydrocarbon, but at
reactor (which may accomplish primarily de
the same time to convert normal butane to iso
aromatizing if the feed stock is not su?‘iciently
butane, a portion of which may be withdrawnand
dearomatized or otherwise may accomplish a part
used in other reactions.
35 of the averaging) and the lower layer from a
The butanes separated for recycling may be de
second stage reactor (which may act upon the
propanized by fractional distillation, absorption,
upper layer from the ?rst stage to accomplish
or any other fractionation or suitable method
averaging) may be combined and fed to a cata
before recycling, if the propane builds up to an
lyst recovery tower from which the ?uorides are
undesirable level.
'
4.0 removed at the top by distillation and returned
The wanted products may be withdrawn from
to the ?rst and/or second stage reactors.
intermediate plates in the primary fractionating
The following examples are given merely as il-v
column.
lustrative of the results that may be accomplished
The heavier unconverted products may be with
when the invention is practiced on a laboratory
drawn from the bottom of the column. These
scale. This may be transformed on a commercial
may or may not be recycled to the reaction zone,
basis, with the incidental improvements as de
depending upon their character, or they may be
scribed heretofore:
‘
>
‘
'
further fractionated and a part returned to the
reaction zone.
Example 1
Alternatively, the upper layer may be sent to a 50
A kerosene fraction and isobutane gas in the
debutanizer and the heavier material from the
ratio of '7 mols of the latter per mol of the kerosene
bottom of the debutanizer may be treated to re
are treated under a total pressure of 250 pounds
move ?uorides by any known means and this
per square inch for 10 hours at 85° C. with the lid
treated stock then fractionated into gasoline and
unreacted heavier stock in a separate column.
55 uid HF and BFs, the latter in amount of 50 pounds
partial pressure persquare inch. Thirty to ?fty
If desired, a single product, such as isopentane
per cent of the kerosene is converted into hydro
or neo~hexane or a mixture of the two (since little
carbons of gasoline range, depending upon the
if any normal pentane is formed in the process)
duration of treatment.
may be withdrawn from the fractionating column
and all of the lighter and all of the heavier mate 60.
Ewample 2
rials may be recycled to the averaging reaction
zone. This will shift the conditions in the averag
A de-aromatized Pennsylvania kerosene was
ing reaction so as to form primarily the product
averaged with a mixture of normal butane and
being Withdrawn. The averaging process thus
isobutane containing 16 per cent of the latter, by
may be used essentially for making a single 65 liquid hydro?uoric acid as catalyst in which boron
wanted product with the return of all other prod
?uoride is dissolved to partial pressure of 150
pounds per square inch, 6 mols of butanes being
If ?xed gases should accumulate beyond the
employed per mol of kerosene, the temperature
point where they may be reacted under the con
being 32° ‘C. The total pressure was 210 pounds
ditions employed, they may be removed at any 70 per square inch. After two hours 90 per cent by
point in the process.
weight of kerosene was converted to liquid prod
The presence of aromatics in the feed stocks,
ucts 80 per cent of which consisted of a gasoline
particularly in the higher molecular weight frac
boiling in the range 70-410° F. and having an un
tion where they are more apt to be present, is
leaded A. S. T. M. octane number 84. 20 per cent
undesirable because these aromatics are trans
of the total charge was converted to isopentane.
ucts as raw materials.
aeoaoec
11
12
The butanes remaining contained 65 per cent by
volume of isobutane.
Example 3
was averaged with dearomatized Pennsylvania
kerosene. The volume of the butane fraction
A similar kerosene stock was averaged with a
charge was 40.6%. The amount of the hydrogen
fluoride based on the total hydrocarbon charge
was 33.7 volume per cent, and the amount of
mixture of butanes, by liquid HF as catalyst and
BF: dissolved to partial pressure of 150 pounds
per square inch, the temperature being 0° 'C. The
based on the kerosene was 200% and the weight
of the kerosene based on the total hydrocarbon
the boron tri?uoride was such as to provide a
total pressure was 190 pounds per square inch.
partial pressure of 150 pounds per square inch.
After about 2 hours 83.6 volume per cent‘of gaso 10 The total pressure was 200 pounds per square
inch. The hydrocarbons and the catalyst were
line was obtained.
agitated under these conditions at a temperature
Example 4
of 90° F. for one hour. The hydrocarbon phase.
Butane containing 16% isobutane was averaged
upon its separation from the catalyst, was found
with dearomatized Pennsylvania kerosene. The 15 to contain 0.8% of hydrocarbons lighter than
volume of the butane fraction based on the hero“
C4, 53.2% butanes of which 54.4% was isobutane.
sene was 212% and the weight of the kerosene
The hydrocarbons boiling within the range of
based» on the total charge of hydrocarbon was
70° to 300° F. amounted to 21.6%. The hydro~
39.2%. The reaction was continued with agita
carbons boiling within the range of 300°‘ to 400°
tion at a temperature of 40° F. for two hours. 20 F. amounted to 3.4%, and those boiling above
The amount of the hydrogen fluoride employed
400° F. amounted to 10.2%. 8.6% of hydrocar
was 33 volume per cent based on the total
bons was found in the catalyst phase.
hydrocarbon charge, and the amount of the boron
Calculations showed that about 11% of the
tri?uoride was such as to provide a partial’ pres
butane feed entered into the reaction.
sure of 150 pounds per square inch. The total 25
The recovered butane fraction and the frac
pressure was 220 pounds per square inch. At the
tion boiling above 300° F. may be recycled to
conclusion of the reaction the hydrocarbon phase
the averaging zone, resulting in a net consiunp
was separated from the catalyst phase and the
hydrocarbon phase was fractionated. It was
tion of 39.2% of the charge. Of this, 55% is
converted into hydrocarbons in the gasoline
found to contain 0.23% propane and lighter prod 30 range.
ucts, 38.8% butanes, of which 64.6% was isobu
Example 7
tone. The recovered butane fraction was 63.8%
A
butane
fraction
containing 60.9% of iso
of the butane charge, indicating that 36.2% of the
butane was averaged with an Illinois kerosene
butane fraction had entered into the reaction.
The products boiling within the range of 70° to 35 having a boiling range of 340 to 520° F. The
aromatics in the kerosene had been reduced to
300° F. amounted to 28.7%. The products boil~
less than 2% by treatment with hydrogen fluo
ing from 300° F. to 400° F. amounted to 8%, and
ride and boron tri?uoride followed by treatment
the products above 400° F. amounted to 17.6%.
with silicon dioxide. The volume of the butane
The hydrocarbons in the catalyst phase amounted
to 6.2%.
>
If the butanes recovered are recycled, the gaso
line fraction based on the heavy stock and the
butanes reacted would amount to about 47%.
Example‘ 5
A butane fraction containing 11% isobutane
fraction, based on the kerosene, was about 400%
and the weight of the kerosene, based on the
total hydrocarbon charged, was 26.6%. The
amount of hydrogen fluoride was 100 volume per
cent, based on the kerosene charged, and the
amount of boron tri?uoride was such as to pro
vide a partial pressure of 190 pounds per square
inch. Thehydrocarbons and the catalyst were
agitated in the liquid phase at a temperature of
was averaged with a dearomatized Illinois naph
tha. The volume of the butane fraction based
90° F. for 1 hour. The hydrocarbon phase, upon
upon the naphtha was 262% and the weight of
the naphtha based on the total hydrocarbon 50 its separation from the catalyst phase,v was found
charge was 3l.05%. The amount of hydrogen
?uoride based on the hydrocarbon charge was
to contain 1.5% hydrocarbons lighter than C4,
63.6% butanes of which 66.1% was isobutane.
The hydrocarbons boiling within the range of
28.4 volume per cent and the amount of boron
isopentane to 300° F. amounted to 14.7% and
tri?uoride was such as to provide a partial pres
amounted
sure of 150 pounds per square inch. The total 55 the hydrocarbons boiling above 300°
to 9.5%. The catalyst phase contained 5.7%
pressure was 220 pounds per square inch. The
hydrocarbons. The recovered butane fraction
reaction was continued at a temperature of 122°
and the fraction boiling above 300° F. may be
F. for two hours, following which the phases were
recycled, resulting in a net consumption of 21.9%
separated and the hydrocarbon phase fraction
ated. The amount of hydrocarbons lighter than 60 of the charge. Of this 67.1% is converted into
hydrocarbons in the gasoline range.
C4 was found to be 6.5%. The butanes amounted
to 53.1%, of which 41.8% was isobutane. The
Example 8
fraction from 70° to 300° F. amounted to 25.7%,
A butane fraction containing 60.3% isobutane
and the hydrocarbons above this boiling range
amounted to 0.6%. The catalyst phase contained» 65 was averaged with a, dearomatized Pennsylvania
kerosene, all of the constituents of which boiled
8.9% hydrocarbons. Calculation showed that
above 300° F. The volume of the butane fraction
15.5% of' the butane fed into the reaction zone
based on the kerosene, was about 400% and the
had reacted with the naphtha to form products
weight of the kerosene, based on the total hy
in the gasoline range. The recovered butanes
which. amounted to 58.1% of the charge were re 70 drocarbon charge, was 26.2%. The amount of
the hydrogen ?uoride was 100 volume per cent,
cycled and the gasoline formed, based on the
based on the kerosene charged. The amount of
remaining 41.9%,‘amountedto about 62%.
boron tri?uoride was such as to provide a partial
Example 6
pressure of 150 pounds per square inch. The hy
A butane fraction containing 15.7% isobutane 75 droca-rbons and the catalyst were agitated under
2,405,996
13
these conditions at a temperature of 90° F. for 1
hour, following which the hydrocarbon phase
was strati?ed and separated from the catalyst
phase. The hydrocarbon phase was found to
contain 0.8% of hydrocarbons lighter than C4,
66.5% of butanes, of which 68.3% was isobutane.
The hydrocarbons boiling in the gasoline range,
namely from isopentane to 300° F. amounted to
19.6% and the hydrocarbons boiling above 300°
F. amounted to 9.3%. The catalyst phase con
tained 3.8% hydrocarbons.
14'
ier fractions resulting from a net consumption of
said light normal hydrocarbons and said heavier
hydrocarbons.
‘2. A process of catalytically averaging hydro~
carbons, which comprises reacting a normally
liquid hydrocarbon fraction comprising para?inic
hydrocarbons, and a normally gaseous hydrocar
bon fraction comprising a normally gaseous nor
mal para?inic hydrocarbon, in the presence of a
10 liquid catalyst the inorganic ingredients of which
Upon recycling of
comprise essentially liquid hydrogen ?uoride in
the recovered butane fraction and the fraction
boiling above 300° F. the resulting net consump—
tion of butanes was 7.3% and the kerosene was
which is dissolved not over 50 mol per cent of
16.9% or a total of 24.2%.
‘boron tri?uoride, and continuing the reaction
under a pressure to maintain the hydrogen ?uo
Of this 81% was con~ 15 ride liquid and at a temperature and for a period
verted into hydrocarbons in the gasoline range.
The above examples are given merely as illus
trative of the results that may be accomplished
and not as a limitation upon the scope of the in
vention as described heretofore.
From the above explanation it seems likely that
the normal hydrocarbon in the lower molecular
weight hydrocarbon feed is isomerized, that the
higher hydrocarbon fraction is cracked, and that
the unsaturates formed in the cracking are used
in alkylating the isomer. It is surprising that all
three of the reactions can be effected simultane
ously under the same conditions, since it has been
of time while regulating the activity of the cata
lyst by adjusting the partial pressure of the boron
tri?uoride to produce hydrocarbons intermediate
said liquid and said gaseous hydrocarbon frac
tions resulting from a net consumption of said
liquid hydrocarbon fraction and said normally
gaseous normal para?inic hydrocarbon.
3. A process of catalytically averaging hydro
carbons which comprises reacting a normally liq
uid hydrocarbon fraction comprising para?inic
hydrocarbons, and a normally gaseous hydrocar
bon fraction comprising'normal butane, in the
presence of a liquid catalyst the inorganic in
thought that more vigorous conditions are re
gredients of which comprise essentially liquid hy
quired for isomerization than for alkylation, and
also that conditions which crack the upper frac
drogen ?uoride inv which is dissolved not over 50
mol per cent of boron tri?uoride, and continu
tion would prevent the alkylation (i. e. crack the _
alkylate as fast as it is formed). That the aver
ing the reaction under a pressure to maintain the
aging is possible is attributed to the catalyst used
in this particular reaction and the ability to con
trol its activity in relation to the other conditions
so as to obtain the averaging reaction.
hydrogen fluoride liquid and at a temperature
and for a period of time while regulating the
activity of the catalyst by adjusting the partial
pressure of the boron tri?uoride to produce hy
drocarbons intermediate said liquid and said gas
It will be apparent that the control of the proc
eous hydrocarbon fractions resulting from a net
ess is an important aspect of the invention and
that it is not possible to interrelate the variables
mathematically. However, it is believed that one
skilled in the art, in view of the disclosure in
consumption of said. liquid hydrocarbon fraction
this application, will be able to adjust the condi
tions without di?iculty so as to obtain the desired
new results.
The reference to a “hydrocarbon fraction” is
intended to refer to a pure hydrocarbon as well
as a mixture of hydrocarbons.
This application is a continuation-in-part of
applications Serial Nos. 423,073 and 458,769, ?led
December 15, 1941 and September 18, 1942, re
spectively.
It will be apparent that the invention is capa
ble of many applications and variations and I
intend all of them to be included as are within
the following claims.
I claim:
and said normal butane.
4. A process of catalytically averaging hydro
carbons which comprises reacting a butane frac
tion containing normal butane and a heavier
hydrocarbon fraction higher than gasoline in the
presence of a liquid catalyst, said catalyst com
prising essentially liquid hydrogen ?uoride in
which is dissolved less than 50 mol per cent of
boron tri?uoride as the primary inorganic cata
lytic ingredients, and continuing the reaction un
der a pressure to maintain the hydrogen ?uoride
and the hydrocarbons liquid and at a tempera
ture and for a period of time while regulating
the activity of the catalyst by adjusting the par
tial pressure of the boron tri?uoride to produce
gasoline resulting from a net consumption of said
normal butane and said heavier fraction.
5. A process of catalytically averaging hydro
1. A process of catalytically averaging hydro
carbons, which comprises reacting kerosene and
carbons which comprises reacting a light hydro~
a normally gaseous hydrocarbon fraction com
carbon fraction comprising normal hydrocarbons 60 prising normal butane, in the presence of a liq
of not over six carbon atoms and a heavier hydro
uid catalyst the inorganic ingredients of which
carbon fraction comprising primarily hydrocar
comprise essentially liquid hydrogen ?uoride in
bons having at least two more carbon atoms than
contained in said light fraction in the presence
of a liquid catalyst, said catalyst comprising es
sentially liquid hydrogen ?uoride in which is dis
which is dissolved not over 50 mol per cent of
boron tri?uoride, and continuing the reaction
under a pressure to maintain the hydrogen ?uo
ride liquid and at a temperature and for a period
solved less than 50 mol per cent of boron tri
of time while regulating the activity of the cata
?uoride as the primary inorganic catalytic in
lyst by adjusting the partial pressure of the boron
gredients, and continuing the reaction under a
trifluoride to produce hydrocarbons intermedi
pressure to maintain the hydrogen ?uoride and 70 ate said kerosene and said gaseous hydrocarbon
the hydrocarbons liquid and at a temperature
fraction resulting from a net consumption of said
and for a period of time while regulating the
kerosene and said normal butane.
6. A process of catalytically averaging hydro
activity of the catalyst by adjusting the partial
pressure of the boron tri?uoride to produce hy
carbons, which comprises reacting a normally
drocarbons intermediate said light and said heav
liquid hydrocarbon fraction comprising paraffinic
2,405,996
15
carbons which comprisesreacting a butane frac
tion and a heavier hydrocarbon fraction having
at least six carbon atoms in the presence of a
liquid catalyst, said catalyst comprising essen
ingredients of which comprise essentially liquid
hydrogen ?uoride in which is dissolved not over Q1. tially liquid hydrogen ?uoride in which is dis
solved less than 50 mol per cent of boron tri
50 mol per cent of boron tri?uoride, and con
?uoride as the primary inorganic catalytic in
tinuing the reaction under a pressure to main
gredients, and in the presence or" a complex in
tain‘ the hydrogen ?uoride liquid and at a tem
said liquid catalyst phase formed by the action
perature and for a period of time while regulat
ing the activity of the catalyst by adjusting the 10 of the ?uorides upon unsaturated hydrocarbons,
and continuing the reaction under a pressure to
partial pressure of the boron tri?uoride to pro
hydrocarbons, and a normally gaseous hydrocar
Fbon fraction comprising normal and isobutanes,
in the presence of a liquid catalyst the inorganic
duce hydrocarbons intermediate said liquid and
maintain the hydrogen ?uoride and the hydro
7. A process of catalytically averaging hydro
carbons, which comprises reacting kerosene and
of the boron tri?uoride to produce hydrocarbons
which comprise essentially liquid hydrogen fluo
carbons, which comprises reacting kerosene and
ride in which is dissolved not over 50 mol per
cent of boron tri?uoride, and continuing the re
action under a pressure to maintain the hydro
a normally gaseous hydrocarbon fraction com,
prising normal butane, in the presence of an un
carbons liquid and at a temperature and for
said butanes resulting from a net consumption
a. period of time while regulating the activity
of said liquid hydrocarbon fraction and said nor
15 of the catalyst by adjusting the partial pressure
mal butane.
intermediate said butane and said heavier frac
tions vresulting from a net consumption of said
a normally gaseous hydrocarbon fraction com
butane and said heavier fractions.
prising normal and isobutanes, in the presence
11. A process of catalytically averaging hydro
of a liquid catalyst the inorganic ingredients of 20
saturated hydrocarbon and a liquid catalyst the
inorganic ingredients of which comprise essen
tially liquid hydrogen ?uoride in which is dis
solved not over 50 mol percent of boron tri?uo
the catalyst by adjusting the partial pressure of
ride, and continuing the reaction under a pres
the boron tri?uoride to produce hydrocarbons
sure to maintain the hydrogen ?uoride liquid and
intermediate said kerosene and said butane re
sulting from a net consumption of said kerosene 30 at a temperature and for a period of time while
gen ?uoride liquid and at a temperature and for
a period of time while regulating the activity of
and said normal butane.
l
8. A process of catalytically averaging hydro
carbons which comprises reacting a light hydro
carbon fraction comprising normal hydrocarbons
of not over six carbon atoms and a heavier hy
regulating the activity of the catalyst by adjust
ing the partial pressure of the boron tri?uoride
to produce hydrocarbonsintermediate said kero
sene and said gaseous hydrocarbon fraction re
sulting from a net consumption of said kerosene
and said normal butane.
12. A process of catalytically averaging hydro
carbons having at least two more carbon atoms
carbons, which comprises reacting gas oil and
than contained in said light fraction in the pres
a normally gaseous hydrocarbon fraction com
ence of a liquid catalyst, said catalyst compris
ing essentially liquid hydrogen ?uoride in which 40 prising a normally gaseous normal para?inic
hydrocarbon, in the presence of a liquid catalyst
is dissolved less than 50 mol per cent of boron
the inorganic ingredients of which comprise es
tri?uoride as the primary inorganic catalytic in
sentially liquid hydrogen ?uoride in whichis dis
gredients, and in the presence of a complex in
solved not over 50 mol per cent of boron tri
said liquid catalyst phase formed by the action
?uoride, and continuing the reaction under a
of the ?uorides upon unsaturated hydrocarbons,
pressure to maintain the hydrogen ?uoride liquid
and continuing the reaction under a pressure to
and at a temperature and for a period of time
maintain the hydrogen ?uoride and the hydro
while regulating the activity of the catalyst by
carbons liquid and at a temperature and for a
adjusting the partial pressure of the boron tri
period of time while regulating the activity of
the catalyst by adjusting the partial pressure of 50 ?uoride to produce hydrocarbons intermediate
said gas oil and said gaseous hydrocarbon frac
the boron tri?uoride to produce hydrocarbons
tion resulting from a net consumption of said
intermediate said light and said heavier frac
gas oil and said normally gaseous normal par
tions from a net consumption of said light and
drocarbon fraction comprising primarily hydro
said heavier fractions.
‘
9. A process of catalytically averaging hydro
carbons,‘ which comprises reacting a normally
liquid hydrocarbon fraction comprising paraf?nic
a?inic hydrocarbon.
13. A process of catalytically averaging hydro
carbons, which comprises reacting a light hydro
carbon fraction comprising normal hydrocar
. icons of not over six carbon atoms and a heavier
hydrocarbons, and a normally gaseous hydro
hydrocarbon fraction comprising primarily hy
carbon fraction comprising‘ a normally gaseous
normal para?mic hydrocarbon, in the presence 60 drocarbons having at least two more carbon
atoms than contained in said light fraction in a
of an unsaturated hydrocarbon and a liquid cata
reaction zone in the presence of a liquid cata
lyst the inorganic ingredients of‘which comprise
lyst, said catalyst comprising essentially liquid
essentially liquid hydrogen ?uoride in which is
hydrogen ?uoride in which is dissolved less than
dissolved not over 50 mo] per cent of boron tri
?uoride, and continuing the reaction under a I‘ 50 mol per cent of boron tri?uoride as the pri
mary inorganic catalytic ingredients, and con
pressure to maintain the hydrogen ?uoride liquid
and at a temperature and for a period of time
tinuing the reaction under a pressure to main
tain the hydrogen ?uoride and the hydrocarbons
while regulating the activity of the catalyst by
liquid and at a temperature and for a period of
adjusting the partial pressure of the boron tri
?uoride to produce hydrocarbons intermediate 70 time while regulating the activity of the catalyst
by adjusting the partial pressure of the boron
said liquid and said gaseous hydrocarbon frac
tri?uoride to produce hydrocarbons intermediate
tions resulting from a net consumption of said
said light and said heavier fractions from a net
liquid hydrocarbon fraction and said normally
consumption of said light and said heavier frac
gaseous normal paraf?nic hydrocarbon.
10; A process of catalytically averaging hydro 75 tions, separating the catalyst phase and the hy
2,405,996
17
dro'carbon phase, and'recycling the catalystpha’se
to the averaging reactionKzon'e.
" i
e
-
"
V
18,
whichis dissolved?less than 5011101 per cent
of’ boron ‘tri?uoride as - the primary inorganic
7 14. _A process of catalytically averaging hy
drocarbons, which comprises reacting a light hy
drocarbon fraction comprising normal hydrocar
?uoride and the hydrocarbons, liquid and at a
bons of not over six carbon atoms and a heavier
temperature and for a period of time while reg
hydrocarbon fraction comprising primarily hy
catalytic ingredients, and continuing-the reac
tion under a pressure to maintain the hydrogen
ulating the activity of thecatalyst by adjusting
drocarbons having at least two more carbon atoms
than contained in said light fraction in a reaction
the partial pressure of the boron tri?uoride to
produce hydrocarbonsinterm'ediate said butane
zone in the presence of a liquid‘catalyst; said 10 and said heavier fractions resulting-from a net
catalyst comprising essentially liquid hydrogen
consumption of said butane and said heavier frac
?uoride in which is dissolved less than 50 mol per
tions,__ separating the hydrocarbons‘, from the
cent of boron tri?uoride as the primary inorganic
catalyst phase,‘ fractionating the hydrocarbons
catalytic ingredients, and continuing the reac
and recycling the unreacted butane fraction to
tion under a pressure to maintain the hydrogen 15 the averaging reaction zone.
‘
fluoride and the hydrocarbons liquid and at a
18. A process of catalytically averaging hydro
temperature and for a period of time while regu
carbons, which comprises reacting a light hydro
lating the activity of the catalyst by adjusting the
carbon fraction comprising normal hydrocarbons
partial pressure of the boron tri?uoride to pro
of not over six carbon atoms and a heavier hy
duce hydrocarbons intermediate said light and 20 drocarbon fraction comprising primarily hydro
said heavier fractions from a net consumption
carbons having at least two more carbon atoms
of said light and said heavier fractions, separat
than contained in said light fraction in a reac
ing the ?uorides from the catalyst phase and re
tion zone in the presence of a liquid catalyst, said
cycling the separated ?uorides to the averaging
catalyst comprising essentially liquid hydrogen
reaction zone.
25 ?uoride in which is dissolved less than 50 mol
15. A process of catalytically averaging hydro
per cent of boron tri?uoride as the primary inor
carbons which comprises reacting a butane frac
ganic catalytic ingredients, and continuing the
tion and a heavier hydrocarbon fraction having
reaction under a pressure to maintain the hy
at least six carbon atoms in a reaction zone in the
drogen ?uoride and the hydrocarbons liquid and
presence of a liquid catalyst, said catalyst com 30 at a temperature and for a period of time while
prising essentially liquid hydrogen ?uoride in
regulating the activity of the catalyst by adjust
which is dissolved less than 50 mol per cent of
ing the partial pressure of the boron tri?uoride
boron tri?uoride as the primary inorganic cata
to produce hydrocarbons intermediate said light
lytic ingredients, and continuing the reaction un
and said heavier fractions from a net consump
der a pressure to maintain the hydrogen ?uoride
tion of said light and heavier fractions, separat
and the hydrocarbons liquid and at a temperature
ing the catalyst phase and the hydrocarbon
and for a period of time while regulating the
phase, fractionating the hydrocarbon phase to
activity of the catalyst by adjusting the partial
separate a single wanted close boiling fraction,
pressure of the boron tri?uoride to produce hy
and recycling at least part of'the light and the
drocarbons intermediate said butane and said 40 heavier hydrocarbons to the averaging reaction
heavier fractions resulting from a net consump
tion of said butane and said heavier fractions,
separating the ?uorides from the catalyst phase,
and recycling the separated ?uorides to the aver
aging reaction zone.
16. A process of catalytically averaging hydro
carbons, which comprises reacting a light hy
drocarbon fraction comprising normal hydrocar
bons of not over six carbon atoms and a heavier
hydrocarbon fraction comprising primarily hy
zone.
19. A process of catalytically averaging hydro-‘
carbons which comprises mixing 1 to 6 mols of
a light hydrocarbon fraction comprising normal
hydrocarbons of not over six carbon atoms with
1 mol of a heavier hydrocarbon fraction com
prising primarily hydrocarbons having at least
two more carbon atoms than contained in the
light fraction in a reaction zone in the presence
of a liquid catalyst, said catalyst comprising es
sentially liquid hydrogen ?uoride in which is dis
drocarbons having at least two more carbon atoms
than contained in said light fraction in a reaction
zone in the presence of a liquid catalyst, said cata
solved less than _50 mol per cent of boron tri
lyst comprising essentially liquid hydrogen ?uo
gredients, and in the presence of a complex in
ride in which is dissolved less than 50 mol percent
of boron tri?uoride as the primary inorganic cata
lytic ingredients, and continuing the reaction
under a pressure to maintain the hydrogen ?uo
ride and the hydrocarbons liquid and at a tem
perature and for a period of time while regulat
said liquid catalyst phase formed by the action of
the ?uorides upon unsaturated hydrocarbons,
ing the activity of the catalyst by adjusting the
partial pressure of the boron tri?uoride to pro
duce hydrocarbons intermediate said light and
said heavier fractions from a net consumption
of said light and said heavier fractions, separat
ing the catalyst phase, fractionating the hydro
carbon phase and recycling any unreacted light
hydrocarbon fraction to the averaging reaction
?uoride as the primary inorganic catalytic in
and continuing the reaction under a pressure to
maintain the hydrogen ?uoride and the hydro
carbons liquid and at a temperature and for a
period of time while regulating the activity of
the catalyst by adjusting the partial pressure of
the boron tri?uoride to produce hydrocarbons in
termediate said light and said heavier fractions
, resulting from a net consumption of said normal
'hydrocarbons and said heavier hydrocarbons,
separating the hydrocarbon and. the catalyst
phase, fractionating the hydrocarbons to sepa- '
rate a close boiling fraction and recycling at
least some of the unreacted hydrocarbons lighter
1'7. A process of catalytically averaging hy 70 than said close boiling range to the averaging
drocarbons which comprises reacting a butane
reaction zone, separating the ?uorides from at
zone.
fraction and a heavier hydrocarbon fraction hav
ing at least six carbon atoms in a reaction zone
in the presence of a liquid catalyst, said catalyst
least part of the catalyst phase and recycling the
separated ?uorides to the averaging reaction
comprising essentially liquid hydrogen ?uoride
20. Aprocess of catalytically averaging hydro
zone.
-
$9519.96
19
20
carbons, which comprises mixing’ 1’ to 6' mols of
abutane fraction containingjnormal butane with
carbons liquid and ‘at a temperature and for a
l molof‘ a heavier hydrocarbon fraction higher
than gasoline in a reaction zone in the presence
of a liquid; catalyst, said catalyst comprising es
sentially liquid hydrogen ?uoride in which is dis
solved less than 50 mol per cent of boron tri?uo
period of time while‘regulating the activity of
the catalyst ‘by adjusting; thepartial pressure of
the boron \tri?uoride to producer gasoline resulting
from a net consumption of said normalbutane
and said heavier fraction, separating the hydro
carbon and the catalyst phase, separating ?uo
ride as the primary inorganic catalytic ingredi
rides from the catalyst phase and recycling the
ents, ‘and in the presence of a complex in said
separated ?uorides to the. vaveraging reaction
liquid catalyst phase formed by the action of the 10 zone, fractionating the hydrocarbon phase and
recycling at least part of the excess of the butane
?uorides upon unsaturated hydrocarbons, and
fraction to theaverag'ing reaction zone.
‘
‘continuing the reaction ‘under a pressure to
maintain the hydrogen ?uoride and the hydro
I ROBERT E. BURK.
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